Fluoride-Based Deep Eutectic Solvents with Amide Dual-Hydrogen-Bond Donors.

Developing F--containing electrolytes is crucial for electrochemical and chemical fluorination. However, balancing the F- concentration and electrochemical stability of the electrolytes remains a challenge. In this study, fluoride-based deep eutectic solvents (F-DESs) were obtained by using amide hydrogen-bond donors (HBDs) containing dual N-H bonds. The obtained F-DES, [TMA]F·3.5[1,3-DMU], was prepared by facilely mixing solid compounds of tetramethylammonium fluoride ([TMA]F) and 1,3-dimethylurea (1,3-DMU), resulting in a high F- concentration (2.6 mol dm-3) and a wide electrochemical window (3.1 V) at room temperature. The electrochemical window was much wider than that of [TMA]F·3.5[EG] (EG, ethylene glycol) as another F-DES with an alcohol HBD (1.9 V). Moreover, [TMA]F·3.5[1,3-DMU] exhibited an ionic conductivity that was 2 orders of magnitude higher than that of [TMA]F·3.5[1,3-DMTU] (1,3-DMTU, 1,3-dimethylthiourea) around room temperature because of the bifurcated hydrogen bonds between the dual N-H bonds of 1,3-DMU and one F-. Thus, [TMA]F·3.5[1,3-DMU] was demonstrated to be applicable to electrochemical fluorination.

A 3.2 V Binary Layered Oxide Cathode for Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) can offer high energy density, cyclability, and operational safety while being economical due to the natural abundance of potassium. Utilizing graphite as an anode, suitable cathodes can realize full cells. Searching for potential cathodes, this work introduces P3-type K0.5Ni1/3Mn2/3O2 layered oxide as a potential candidate synthesized by a simple solid-state method. The material works as a 3.2 V cathode combining Ni redox at high voltage and Mn redox at low voltage and exhibits highly reversible K+ ion (de)insertion at ambient and elevated (40-50 °C) temperatures. First-principles calculations suggest the ground state in-plane Mn-Ni ordering in the MO2 sheets is strongly correlated to the K-content in the framework, leading to an interwoven and alternative row ordering of Ni-Mn in K0.5Ni1/3Mn2/3O2. Postmortem and electrochemical titration reveal the occurrence of a solid solution mechanism during K+ (de)insertion. The findings suggest that the Ni addition can effectively tune the electronic and structural properties of the cathode, leading to improved electrochemical performance. This work provides new insights in the quest to develop potential low-cost Co-free KIB cathodes for practical applications in stationary energy storage.

Honeycomb-Layered Oxides With Silver Atom Bilayers and Emergence of Non-Abelian SU(2) Interactions.

Honeycomb-layered oxides with monovalent or divalent, monolayered cationic lattices generally exhibit myriad crystalline features encompassing rich electrochemistry, geometries, and disorders, which particularly places them as attractive material candidates for next-generation energy storage applications. Herein, global honeycomb-layered oxide compositions, Ag2 M2 TeO6 ( M = Ni , Mg , etc $M = \rm Ni, Mg, etc$ .) exhibiting Ag $\rm Ag$ atom bilayers with sub-valent states within Ag-rich crystalline domains of Ag6 M2 TeO6 and Ag $\rm Ag$ -deficient domains of Ag 2 - x Ni 2 TeO 6 ${\rm Ag}_{2 - x}\rm Ni_2TeO_6$ ( 0 < x < 2 $0 < x < 2$ ). The Ag $\rm Ag$ -rich material characterized by aberration-corrected transmission electron microscopy reveals local atomic structural disorders characterized by aperiodic stacking and incoherency in the bilayer arrangement of Ag $\rm Ag$ atoms. Meanwhile, the global material not only displays high ionic conductivity but also manifests oxygen-hole electrochemistry during silver-ion extraction. Within the Ag $\rm Ag$ -rich domains, the bilayered structure, argentophilic interactions therein and the expected Ag $\rm Ag$ sub-valent states ( 1 / 2 + , 2 / 3 + $1/2+, 2/3+$ , etc.) are theoretically understood via spontaneous symmetry breaking of SU(2)× U(1) gauge symmetry interactions amongst 3 degenerate mass-less chiral fermion states, justified by electron occupancy of silver 4 d z 2 $4d_{z^2}$ and 5s orbitals on a bifurcated honeycomb lattice. This implies that bilayered frameworks have research applications that go beyond the confines of energy storage.

Optical Study of the Surface Film Formed during Li-Metal Deposition and Dissolution Investigated by Surface Plasmon Resonance Spectroscopy.

The features of the electrode surface film during Li-metal deposition and dissolution cycles are essential for understanding the mechanism of the negative electrode reaction in Li-metal battery cells. The physical and chemical property changes of the interface during the initial stages of the reaction should be investigated under operando conditions. In this study, we focused on the changes in the optical properties of the electrode surface film of the negative electrode of a Li-metal battery. Cu-based electrochemical surface plasmon resonance spectroscopy (EC-SPR) was applied because of its high sensitivity to optical phenomena on the electrode surface and its stability against Li-metal deposition. The feature of SPR reflectance dip depends on the optical properties of the electrode surface; namely, the wavelength and depth of the reflectance dip directly connected the refractive index and extinction coefficient (color of electrode surface film), which was confirmed by reflectance simulation. In the operando EC-SPR experiment, various changes in optical properties were clearly observed during the cycles. In particular, the change in the extinction coefficient was more remarkable at the second process than the first process of Li-metal deposition. By electrochemical quartz-crystal microbalance (EQCM) measurements, surface film formation was confirmed during the first Li-metal deposition process. The remarkable change in the extinction coefficient is based on the color change of the surface film, which is caused by the chemical condition change during Li-metal deposition cycles.

Mixed alkali-ion transport and storage in atomic-disordered honeycomb layered NaKNi2TeO6.

Honeycomb layered oxides constitute an emerging class of materials that show interesting physicochemical and electrochemical properties. However, the development of these materials is still limited. Here, we report the combined use of alkali atoms (Na and K) to produce a mixed-alkali honeycomb layered oxide material, namely, NaKNi2TeO6. Via transmission electron microscopy measurements, we reveal the local atomic structural disorders characterised by aperiodic stacking and incoherency in the alternating arrangement of Na and K atoms. We also investigate the possibility of mixed electrochemical transport and storage of Na+ and K+ ions in NaKNi2TeO6. In particular, we report an average discharge cell voltage of about 4 V and a specific capacity of around 80 mAh g-1 at low specific currents (i.e., < 10 mA g-1) when a NaKNi2TeO6-based positive electrode is combined with a room-temperature NaK liquid alloy negative electrode using an ionic liquid-based electrolyte solution. These results represent a step towards the use of tailored cathode active materials for "dendrite-free" electrochemical energy storage systems exploiting room-temperature liquid alkali metal alloy materials.

Electrochemical Surface Plasmon Resonance Spectroscopy for Investigation of the Initial Process of Lithium Metal Deposition.

The initial process of Li-metal electrodeposition on the negative electrode surface determines the charging performance of Li-metal secondary batteries. However, minute depositions or the early processes of nucleation and growth of Li metal are generally difficult to detect under operando conditions. In this study, we propose an optical diagnostic approach to address these challenges. Surface plasmon resonance (SPR) spectroscopy coupled with electrochemical operation is a promising technique that enables the ultrasensitive detection of the initial stage of Li-metal electrodeposition. The SPR is excited in a thin copper film deposited on a glass substrate, which also serves as a current collector enabling electrochemical Li-metal deposition. For a propylene carbonate (PC)-based Li-ion battery electrolyte, under both cyclic voltammetry and constant-current operation, Li-metal deposition is readily detected by changes in the SPR absorption dip in the reflectance spectrum. Electrochemical SPR is highly sensitive to metal deposition, with a demonstrated capability of detecting an average thickness of approximately 0.1 nm, corresponding to a few atomic layers of Li. To identify the growth mechanism, the SPR reflectance spectra of various possible Li-metal deposition processes were simulated. Comparison of the simulated spectra with the experimental data found good agreement with the well-known nucleation and growth model for Li-metal deposition from PC-based electrolytes. The demonstrated operando electrochemical SPR measurement should be a valuable tool for basic research on the initial Li-metal deposition process.

Ether-Functionalized Pyrrolidinium-Based Room Temperature Ionic Liquids: Physicochemical Properties, Molecular Dynamics, and the Lithium Ion Coordination Environment.

The physicochemical properties of room temperature ionic liquids (RTILs) consisting of bis(trifluoromethanesulfonyl)amide (TFSA- ) combined with 1-hexyl-1-methylpyrrolidinium (Pyr1,6+ ), 1-(butoxymethyl)-1-methylpyrrolidinium (Pyr1,1O4+ ), 1-(4-methoxybutyl)-1-methyl pyrrolidinium (Pyr1,4O1+ ), and 1-((2-methoxyethoxy)methyl)-1-methylpyrrolidinium (Pyr1,1O2O1+ ) were investigated using both experimental and computational approaches. Pyr1,1O2O1 TFSA, which contains two ether oxygen atoms, showed the lowest viscosity, and the relationship between its physicochemical properties and the position and number of the ether oxygen atoms was discussed by a careful comparison with Pyr1,1O4 TFSA and Pyr1,4O1 TFSA. Ab initio calculations revealed the conformational flexibility of the side chain containing the ether oxygen atoms. In addition, molecular dynamics (MD) calculations suggested that the ion distributions have a significant impact on the transport properties. Furthermore, the coordination environments of the Li ions in the RTILs were evaluated using Raman spectroscopy, which was supported by MD calculations using 1000 ion pairs. The presented results will be valuable for the design of functionalized RTILs for various applications.

Correction: The effects of the position of the ether oxygen atom in pyrrolidinium-based room temperature ionic liquids on their physicochemical properties.

Correction for 'The effects of the position of the ether oxygen atom in pyrrolidinium-based room temperature ionic liquids on their physicochemical properties' by Kazuki Yoshii et al., Phys. Chem. Chem. Phys., 2020, DOI: .

The effects of the position of the ether oxygen atom in pyrrolidinium-based room temperature ionic liquids on their physicochemical properties.

Room temperature ionic liquids (RTILs) containing ether oxygen atoms have been investigated for a gamut of science and technology applications owing to their superior physicochemical properties. However, the effect of the position of the ether oxygen atom in the side chain on their physicochemical properties is not clearly understood. This study investigates, using both experimental and computational approaches, the effect of ether oxygen atoms on the physicochemical properties of RTILs consisting of bis(trifluoromethylsulfonyl)amide (TFSA-) with 1-methyl-1-propylpyrrolidinium (MPP+), 1-butyl-1-methylpyrrolidinium (BMP+), 1-methoxymethyl-1-methylpyrrolidinium (MOMMP+), 1-ethoxymethyl-1-methylpyrrolidinium (EOMMP+), and 1-methoxyethyl-1-methylpyrrolidinium (MOEMP+). The viscosity of the RTILs containing the ether oxygen atom was lower than that of the alkyl analogues. Moreover, the viscosity of EOMMPTFSA was lower than that of MOEMPTFSA, albeit EOMMPTFSA and MOEMPTFSA have the same molecular weight with ether oxygen atoms at different positions. Ab initio calculations reveal that the number of methylene groups between nitrogen and oxygen atoms in the cation structure profoundly impacts the local stable structure of the cation. Furthermore, we discussed the relationship between the transport properties and the spatial distribution of ions obtained by MD simulations. This result will be valuable in the design of functionalized RTILs, via the judicious tuning of the conformational flexibility of ether oxygen atoms in related ionic liquids.

New insight derived from a two-compartment cell: electrochemical behavior of FeF3 positive electrode.

A designed two-compartment cell was applied to the degradation analysis of FeF3 having high theoretical energy density. Comparing with the result of the coin cell, the two-compartment cell gave us insight that the elution of Fe was responsible for the degradation of FeF3 and LiDFOB was found as an essentially effective additive for suppressing the degradation of FeF3.

Development of a half-cell for x-ray structural analysis of liquid electrolytes in rechargeable batteries.

A half-cell of the rechargeable Li-ion battery was developed to characterize an electrolyte structure using high energy x-ray total scattering measurements in combination with a two-dimensional x-ray detector. The scattering pattern consisted of strong Bragg peaks from electrodes and diffuse scatterings from sapphire windows, in addition to a weak halo pattern from the electrolyte. By selectively removing the signals of the electrodes and windows using specific numerical procedures, we could successfully extract the structural information of the electrolyte, which was in reasonable agreement with the reference data obtained from the electrolyte in a glass capillary. The present demonstration with a half-cell is expected to shed new light on operand characterization of the electrolyte structure during charging and discharging.

A high voltage honeycomb layered cathode framework for rechargeable potassium-ion battery: P2-type K2/3Ni1/3Co1/3Te1/3O2.

The designing of high voltage cathode materials is critical for the advancement of potassium-ion (K-ion) battery. Herein, we present a new honeycomb framework P2-type K2/3Ni1/3Co1/3Te1/3O2 (or equivalently written as K2NiCoTeO6) which exhibits the highest voltage on record (beyond 4 V versus K+/K) for layered cathode materials. This work will allow for the further development of, particularly, high voltage layered cathodes for K-ion battery.

Rechargeable potassium-ion batteries with honeycomb-layered tellurates as high voltage cathodes and fast potassium-ion conductors.

Rechargeable potassium-ion batteries have been gaining traction as not only promising low-cost alternatives to lithium-ion technology, but also as high-voltage energy storage systems. However, their development and sustainability are plagued by the lack of suitable electrode materials capable of allowing the reversible insertion of the large potassium ions. Here, exploration of the database for potassium-based materials has led us to discover potassium ion conducting layered honeycomb frameworks. They show the capability of reversible insertion of potassium ions at high voltages (~4 V for K2Ni2TeO6) in stable ionic liquids based on potassium bis(trifluorosulfonyl) imide, and exhibit remarkable ionic conductivities e.g. ~0.01 mS cm-1 at 298 K and ~40 mS cm-1 at 573 K for K2Mg2TeO6. In addition to enlisting fast potassium ion conductors that can be utilised as solid electrolytes, these layered honeycomb frameworks deliver the highest voltages amongst layered cathodes, becoming prime candidates for the advancement of high-energy density potassium-ion batteries.

Alkali Metal Salts with Designable Aryltrifluoroborate Anions.

Aryltrifluoroborate ([ArBF3](-)) has a designable basic anion structure. Various [ArBF3](-)-based anions were synthesized to create novel alkali metal salts using a simple and safe process. Nearly 40 novel alkali metal salts were successfully obtained, and their physicochemical characteristics, particularly their thermal properties, were elucidated. These salts have lower melting points than those of simple inorganic alkali halide salts, such as KCl and LiCl, because of the weaker interactions between the alkali metal cations and the [ArBF3](-) anions and the anions' larger entropy. Moreover, interestingly, potassium cations were electrochemically reduced in the potassium (meta-ethoxyphenyl)trifluoroborate (K[m-OEtC6H4BF3]) molten salt at 433 K. These findings contribute substantially to furthering molten salt chemistry, ionic liquid chemistry, and electrochemistry.

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries.

A polymer gel electrolyte using AlCl3 complexed acrylamide as a functional monomer and acidic ionic liquid based on a mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl3 (EMImCl-AlCl3, 1-1.5, in molar ratio) as a plasticizer has been successfully prepared for the first time via free radical polymerization. Aluminum deposition is successfully achieved using a polymer gel electrolyte containing 80 wt% ionic liquid. The polymer gel electrolytes are also good candidates for rechargeable aluminum ion batteries.

Physicochemical properties of tri-n-butylalkylphosphonium cation-based room-temperature ionic liquids.

The physicochemical properties of novel four tri-n-butylalkylphosphonium-based room-temperature ionic liquids (RTILs), tri-n-butylmethylphosphonium dimethylphosphate ([P(4,4,4,1)][DMP]), tri-n-butyl(2-hydroxymethyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P(4,4,4,2OH)][Tf2N]), tetra-n-butylphosphonium O,O'-diethylphosphorodithioate ([P(4,4,4,4)][DEPDT]), and tri-n-butyldodecylphosphonium 3,5-bis(methoxycarbonyl)benzenesulfonate ([P(4,4,4,12)][MCBS]), were examined in this study. All RTILs showed a favorable thermal decomposition temperature exceeding 560 K. Of these, [P(4,4,4,12)][MCBS] exhibited a fairly high thermal stability compared with common phosphonium cation-based RTILs reported to date. Interestingly [P(4,4,4,1)][DMP] formed an ionic plastic crystal phase within a range of 279-290 K, but that was not the case with [P(4,4,4,4)][DEPDT], which is similar in the cation and anion structures to the [P(4,4,4,1)](+) and [DMP](-). [P(4,4,4,2OH)][Tf2N] showed a relatively high conductivity of 0.48 mS cm(-1) at 303 K among the RTILs consisting of tri-n-butylalkylphosphonium cation and usual fluoroanion.